Cage-Expansion of Fullerenes

作者：Sheng Zhang, Yoshifumi Hashikawa, Yasujiro Murata · 发表于：Journal of the American Chemical Society · 年份：2021 · DOI：10.1021/jacs.1c05778 · 被引用次数：28 · 研究领域：Fullerene Chemistry and Applications、Carbon Nanotubes in Composites、Graphene research and applications

Despite the first proposal on the cage inflation of fullerenes in 1991, the chemical expansion of fullerenes has been still a formidable challenge. Herein, we provide an efficient methodology to expand [60] and [70]fullerene cages by the inclusion of totally C5N unit, giving nitrogen-containing closed structures as C 65 N and C 75 N with double fused heptagons. This method consists of two steps commenced with the construction of an opening by the reaction with triazine as a C3N source, followed by the cage reformation using N -phenylmaleimide as a C2 source. We also synthesized endohedral cages, demonstrating that the encapsulated H 2 O molecule inside the C 75 N cage prefers the orientation which maximizes the intramolecular interaction with the carbon wall. Additionally, we revealed the existence of a through-space magnetic dipolar interaction between the encapsulated H 2 molecule and the embedded N atom.